JPS63150207A - Chain-prolonged urethanediacrylate and dental impression forming matter - Google Patents

Abstract

Disclosed is a new urethane polyacrylate having at least one terminal isocyanato acrylic pendent radical. Preferably the molecular chain within the acrylate caps has been extended with a polyhydroxy compound just before final end capping with isocyanato acrylic. The isocyanato acrylic is preferably isocyanato ethyl methacrylate and the urethane is diisocyanate capped polyether and the polyether radical is oxyalkylene. The method for producing the urethane polyacrylate involves end capping a polyol with diisocyanate yielding a reaction product with two reactive equivalents of isocyanate and then capping less than all of the isocyanate with a hydroxyacrylate, after which the remaining isocyanate is reacted with polyol to provide chain extension. The chain extending polyol is then capped with a isocyanato acrylic. Also disclosed is a new impression material for application to mammalian tissue and curing in contact therewith; the impression material including a free radical polymerizable resin, alkyl benzensulfonyl titanate, polymerization initiator, and filler; and a method of use.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is particularly useful for making impressions (impressions) of mammalian tissue by tooth application.
The present invention relates to a novel structure of a substance, a urethane diacrylate, which is particularly useful as a compound for a composition for forming a urethane diacrylate, i.e. a composition that precisely corresponds to the tooth surface to be recorded, and to a method for producing the urethane diacrylate. . The present invention furthermore relates to such a novel impression material which is a radically polymerizable resin and contains an alkylbenzenesulfonyl titanate, a polymerization initiator and a filler.

Methods for producing dental impressions are well known, resulting in dental impression materials that can accurately reproduce the surface contours and dimensions of the oral tissues required for denture production. Since the anatomy and products for dentures are usually undercut, preferred impression materials are elastomeric or rubbery materials ranging from gels such as agar or algins to elastomers such as rubbers, silicones and polyethers. It is. Non-aqueous elastomers are preferred because of their excellent dimensional accuracy and their relative stability under ambient conditions. Despite all the improvements that characterize current dental impression materials, they are still extremely limited by clinical factors when used in vivo.

Take two separate pastes (one containing the catalyst, the other containing the promoter), place a measured amount of each on a pad of parchment paper or polyethylene-coated paper, and immediately mix into a substantially even mass. It is known to produce elastomeric impression materials by mixing them with a spatula until they are mixed.

Such impression materials must be used immediately after mixing, and the hardening must be rapid, and at the same time the filling by both agile and non-agile dental professionals must be timely, and the hardening time must be short. Since this is fixed, no matter how careful the dental professional is about the accumulation, special problems cannot be controlled. Moreover, the mixing action tends to introduce air bubbles into the viscous paste, which are difficult to remove and tend to cause surface defects or distortions in the final impression. Mixing is disadvantageous and causes inconsistency.

In normal practice, the dental practitioner uses a saucer containing the paste or a combination of a filling syringe and a saucer to fill the mixed base into the proper location of the tooth tissue. The dental professional or dentist and the patient then use the material until the polymerization reaction has progressed to completion and the material is sufficiently elastic so that the impression can be removed from the tissue without distortion of memory shape or form. , sometimes waiting as long as 10 minutes. The incidence of defective impressions is very high as the patient tends to move spontaneously during this time and throat reflexes are also common. Dental personnel not only lose valuable time and become inactive, but also have time for the re-moulding that is often required.

The materials commonly used to take impressions are described in U.S. Pat.
, 950,300, polyethers as described in U.S. Pat. No. 3,453,242, and American Dental Association Instruction No. 19 ( American Dental
Association 5specification
There are other elastomeric materials whose properties are described in more detail in 19).

Novel urethane polyacrylates with at least one isocyanatoacrylic side group provide excellent dental composition components that, in preferred form, are non-toxic during oral use and provide permanent elastic memory upon curing. It comes to last. New urethane polyacrylate is approximately 360-60
When provided with an initiator activated with actinic radiation in the visible light range of 0 nm, it is stored in the absence of actinic radiation and then filtered to wavelengths restricted to the visible light range. It is substantially stable to permanent memory shape when irradiated with light for 1 minute to cure to a depth of about 2.5 cm (1 inch).

A preferred compound is an extended chain urethane polyacrylate made by the preferred method described below. First, the polyhydroxy compound is reacted with the polyisocyanate to form a first reaction product having about 2 equivalents of reactive isocyanate. The first reaction product is then reacted with less than two equivalents of a compound having an acrylic side group and another reactive site that preferentially reacts with the first reaction product to form a second reaction product. Form. The second reaction product is then reacted with a polyhydroxy compound to form a third reaction product. This third reaction product is then reacted with an isocyanatoacrylate compound to form the urethane polyacrylate of the present invention.

According to another aspect of the invention, a novel impression material is provided for application to mammalian tissue and hardening upon contact therewith to form an impression. The impression material contains a radically polymerizable resin, an alkylbenzenesulfonyl titanate, a polymerization initiator, and a filler. A method of using the novel impression material is also provided.

A preferred embodiment, which is one of the characteristics of the present invention, is a novel structure of a substance in the form of a novel compound having the following general formula: R1-[A]-R1 In the above formula, R8 is or, and R1 is They may be the same or different, and each independently preferably has 5 to 100 carbon atoms, more preferably 5 to 1 carbon carbon.
5, most preferably having 6 to 11 carbons.

R3 is H, alkyl, substituted alkyl, aryl, substituted aryl, F, CN (the term substituted as used in this application means substituted, i.e. at least one C or atom other than H is present) or the presence of a group such as a benzene ring. Acrylic means any acrylic side group; diacrylic means a group or compound with two acrylic side groups.) R3 may be the same or different at each position.

R3 is preferably methyl.

R4 is a divalent hydrocarbon group or a divalent substituted hydrocarbon group, and may be linear, branched, or cyclic, or a combination thereof.

Cyclic is meant to include aromatic and peterocyclic compounds.

R4 preferably has 2 to 100 carbons, more preferably R4 has 2 to 100 carbons, even more preferably 2 to 10 carbons.
, most preferably an aliphatic group having 2 to 6 carbons.

(A) is any polyurethane, polyester or polyether oligomer. (Poly used in the present invention means 2 or more. Oligomer means about 500 to
Means a molecular weight of 5000. The molecular weight of the oligomer and its resulting physical properties can be controlled by careful selection of substituents to prepare the oligomer by methods well known to those skilled in the art. For example, (A) is selected to be a low molecular weight polyether if a relatively hard polymer is desired, or (A) and other substituents are selected to be a relatively soft, flexible polymer if a relatively soft, flexible polymer is desired. is selected to have a high molecular weight. As those skilled in the art will appreciate, the concentration and type of filler used in the polymer, as well as other factors, will to some extent influence the properties of the polymer. Generally, however, if a relatively rigid polymer is desired, the molecular weight of the oligomer will be between about 500 and 2.
000, preferably in the range 650-1500. If a soft flexible polymer is desired, the oligomer has a molecular weight of about 1500 to 5000, preferably about 200
It has a molecular weight within the range of 0-4000.

Soft visible resins have elastic properties and are characterized by typically exhibiting an elongation rate of about 50% or more from a stress-free state to before breaking or tearing after curing.

Rigid polymers are characterized by having an elongation of about 50% or less from an unstressed state before tearing or breaking.

The elongation properties described herein are for unfilled resins.

The term main chain as used in the present invention refers to the oligomeric structure between the two urethane groups closest to the ends of the molecule. ) A presently preferred structure that forms an important aspect of the invention is A
This is a structure when is expressed as (RS←−X −1−R6).

X is polyurethane, and R5-X and R6-X are bonded by urethane or polyurethane bonds.

X may broadly contain any hydrocarbon or substituted hydrocarbon group, and may be linear, branched or cyclic, or a combination thereof, and may also contain one or more of the following groups: siloxane , substituted siloxanes, sulfones, etc., but preferably polyethers, polyesters or combinations thereof, most preferably X is a polyether and the polyether group is linear.

R5 and R6 are each independently a divalent hydrocarbon group or a divalent substituted hydrocarbon group, which may be linear, branched, or cyclic, or a combination thereof, and may be siloxane or substituted siloxane. It's okay. 'Lower alkyl refers to 1 to 25 carbon atoms, preferably 1 to 25 carbon atoms.
15, more preferably alkyl or substituted alkyl having 1 to 12 carbon atoms. Alkylene, unless otherwise specified, means an alkyl group having from 2 to 40 carbon atoms, preferably from 2 to 30 carbon atoms, and most preferably from 2 to 15 carbon atoms.

Substituents are not particularly limited, and typical examples include halogen,
is meant to include groups selected from the group consisting of lower alkyl, oxy-lower alkyl, silyl-lower alkyl, phenyl, halogen phenyl, alkoxy phenyl, thiohalogenmethyl, dihalogenmethyl and similar substituents, where lower alkyl has 1 to 6 carbons.

R5 and R6 preferably have 2 to 100 carbons, more preferably R5 and R6 are aliphatic groups having 2 to 100 carbons, and even more preferably 2 to 10 carbons. R5 and R
6 may be the same or different.

One skilled in the art can adjust the (A) group to achieve the properties of choice. In particular, in a particularly preferred group (A) in which both R5 and R6 are bonded to X through a urethane bond, a particularly preferred advantage is when X has a considerable molecular weight and both R5 and R6 have a low molecular weight. , which constitutes a particularly preferred embodiment of the present invention.

In a preferred embodiment, A is the following group -R-N-C-0-(CH2)4-0-C-N-R-N
-C-[Ra-01x-C-N-R-, where R is alkylene having 2 to 25 carbon atoms, R is preferably the following group, and C8°R8 is 2 to 25 carbon atoms. is an alkylene of -CH
, -CH- is preferably a group I, and X is 10 to CH.

It is 100.

In a preferred embodiment, the polymers of the present invention are broadly described as comprising a polyol/polyisocyanate/hydroxyalkyl methacrylate/dihydroxy compound/isocyanatoacrylate molar ratio of about 1+2:1 to 1.5:0.5 to 1. I can do it.

In a preferred reaction: R1 is preferably a group formed by reacting a hydroxyacrylate with an isocyanate group on a prepolymer polyurethane oligomer, and is described as containing a urethane group formed by an isocyanate, or Groups formed entirely by isocyanatoacrylate when it is reacted with hydroxy groups on the prepolymer polyurethane oligomer.

In (R15←--X-←R6), R5 is the terminal group of the prepolymer polyurethane oligomer when the terminal urethane group is described as part of R1. For clarity of explanation, in Example 1 this is the trimethylhexamethylene group from trimethylhexamethylene diisocyanate and includes other urethane groups formed by the diisocyanate. R6 is 1.
It is an oxyalkyl residue of 4-butanediol.

A more preferred compound has the following formula: CI+30 N OI II
II 1HOOCH-J (R7 is alkylene or substituted alkylene, X is 1
0 to 100): or (R is 2 to 25 carbon atoms, preferably 2 to 15 carbon atoms)
, R8 is alkylene of 2 to 25 carbon atoms, preferably 2 to 8 carbon atoms, and X is 10 to 1
00).

In a preferred method of preparing the novel compounds of the invention, which method forms an important aspect of the invention, a first reaction product is formed by reacting a polybitroxy compound with a polyisocyanate; is reacted with an amount of at least about 1 equivalent of the acrylic group of R1 to leave at least about 1 equivalent of unreacted isocyanate, and this second reaction product is then reacted with an amount of R6 in the unreacted isocyanate portion. Chain extended with a polyhydroxyalkylene, substituted alkylene, arylene, or substituted arylene, the third reaction product is then end-capped with R1 isocyanatoacrylate at the chain lengthening site.

Preferably, the isocyanate and hydroxy-reactive compounds are di- or tri-isocyanates or di- or tri-hydroxy compounds, more preferably diisocyanates and dihydroxy compounds. The equivalent weight used in the present invention means the theoretical reactivity value of one specific group in each molecule.

More generally describing the method of making the novel extended chain urethane polyacrylates of preferred embodiments, a polyhydroxy compound is first reacted with a polyisocyanate to form a first reaction product having about 2 equivalents of reactive isocyanate. form things. This first reaction product is then reacted with less than two equivalents of a compound having an acrylic side group and another reaction site that preferentially reacts with the first reaction product to form a second reaction product. Form. The compounds used in connection with the present invention can be prepared from compounds of other molecular structures or compounds of a plurality of single molecular structures having the above-mentioned characteristics. The use of the term equivalent as used in connection with the present invention (as used in the present invention as less than 2 equivalents) refers to the reaction value under the reaction conditions described above.

The second reaction product is then polyhydroxyalkylene,
Reacted with a compound selected from the group consisting of substituted alkylene, arylene, substituted arylene, oxyalkylene, and substituted oxyalkylene to form a third reaction product. This third reaction product is then reacted with isocyanatoacrylate.

The theoretical reaction to form the first reaction product forms a polyurethane with a group that crosslinks the two urethane groups and leaves other reactive side chain isocyanate reaction sites in the first reaction product. In order to do this, a portion of the reactive isocyanate is blocked. The first reaction product is then reacted with an acrylic compound to leave at least one acrylic side group on at least a substantial portion of the reacted molecular products of the second reaction product. Forced to react. Sufficient substoichiometric amounts of acrylic compound are used to satisfy all isocyanate side groups, so that substantial side chain isocyanate reaction sites remain. The reaction of the side chain isocyanate reactive sites in the second reaction product with the polyhydroxy compound is thought of as a chain lengthening reaction, at least preferentially blocking the reactive isocyanate side groups. Preferably, the first polyhydroxy compound (used in the resulting X) is a dihydroxyoxyalkylene;
The second polyhydroxy compound (residue of R8) is dihydroxyalkylene and the isocyanatoacrylic compound is incyanatoalkylene acrylate.

In another preferred embodiment, the structures of the present invention are generally produced by reacting a polyhydroxy compound with a polyisocyanate to form a first reaction product to produce a polyurethane. Excess polyisocyanate is added to form an isocyanate-terminated prepolymer. A part of the terminal isocyanate group is capped with an acrylic group R3, and the rest is chain extended with 1,4-butanediol. The reaction product of polyisocyanate and hydroxyacrylate is then reacted with a chain-extended prepolymer.

More specifically, the following formula: % formula %) [In the above formula, 0-PE-0 represents a hydroxy-substituted polyether, polyurethane or polyester, OCN and NGO represent an isocyanate group, and -(OCN-NGO)- represents a polyisocyanate, HMA represents an unsaturated hydroxy-substituted organic acid ester, and BD represents a lower alkyl diol. (b) reacting about 1 equivalent of hydroxy-substituted oligomer with about 2 equivalents of diisocyanate to form a polyurethane having primarily an isocyanate group on one end and an unsaturated organic acid ester on the other end; reacting the polyurethane formed in (a) with about 1/2 equivalent of an unsaturated hydroxy-substituted organic acid ester; (c) to form a polyurethane having an unsaturated organic acid ester at one end and a hydroxyl at the other end; Process (
(d) reacting the product of b) with a lower alkyl diol that reacts with said incyanate groups; There is provided a manufacturing method consisting of the steps of reacting the reaction product of step (e) with the polyurethane formed in step (e).

In a preferred method, PE is a polyether, the polyisocyanate is trimethylhexamethylene diisocyanate, HMA is hydroxyethyl methacrylate, and BD is butanediol.

In general, suitable polyhydroxy, poly, isocyanate and acrylate compounds for use in the present invention are described in U.S. Pat. No. 4,182,829, the contents of which are incorporated herein by reference. It is disclosed in numerous documents including . Suitable alkylene isocyanatoacrylate compounds for use in the present invention are disclosed in US Pat. No. 4,233,425, the contents of which are incorporated herein by reference.

The saturated di- or tri-polyhydroxy compounds specifically used to prepare the urethane reaction product X in the practice of this invention consist of any of a variety of materials, particularly polyethers, polyesters, and polycarbonates. Particularly preferred are those having substantially no internal ethylenic unsaturation. One or more materials with two and droxy functional groups without ethylenic unsaturation can also be used.

Preferred materials include aliphatic diols having from about 8 to about 20 carbon atoms between the drooxy functions, such as dodecanediol, decanediol, and the like. Certain prepolymer materials such as polyalkylene ether glycols are even more preferred.

Therefore, materials such as polymethylene ether glycol, polyethylene ether glycol, polypropylene ether glycol, polybutylene ether glycol, etc. can also be used. Those skilled in the art will appreciate that a variety of such ether glycols can be used in the practice of this invention. Preferred materials for use in the present invention are polybutylene ether glycol (also called polytetramethylene ether dalicol) and polypropylene ether glycol. As will be readily understood, the polyalkylene ether glycols can also be commonly used as mixtures of different types having different molecular weights.

It will be apparent that a variety of polyisocyanates can be used in preparing the urethane reaction product of X according to the present invention. For example, hexamethylene diisocyanate,
Examples include tetramethylhexamethylene diisocyanate, isophorone diisocyanate, trimer of isophorone diisocyanate, trimer of 1,6-hexamethylene diisocyanate and many other compounds. - Generally speaking, it has been found that it is most preferable to use aliphatic or cycloaliphatic diisocyanate species. While such non-aromatic polyisocyanates are preferred, toluene diisocyanate and methylene bisphenyl-4-
Aromatic materials such as diisocyanates can also be used. The isocyanate functional groups of the material are separated by multiple carbon atoms. The number of such carbon atoms is about 6 to
About 20 is preferred. The preferred diisocyanate used in the present invention is trimethylhexamethylene diisocyanate.

The glycol is reacted with one or more equivalents of the polyisocyanate, preferably diisocyanate, of the material of the invention so that it usually has an excess of incyanate functionality over glycol functionality. The amount of isocyanate moiety reacted with the hydroxy groups of the glycol mixture is such that the final stoichiometric amount of incyanate is in excess of the hydroxy. This molar excess is from about 50 to about 150%, preferably from about 75 to about 125%.
%. More preferably, about 100% molar excess of isocyanate is present in excess of the molar amount of hydroxy functionality. The isocyanate moieties are included in excess to provide reactive sites for capping and chain extension of the urethane oligomer with the pentapolymerizable acrylic functional group.

The R1 acrylate of the invention is selected from various compounds according to the invention. Preferred acrylates are hydroxyalkylated products of acrylic acid and/or methacrylic acid, such as acrylic acid hydroxyethyl ester, acrylic acid hydroxypropyl ester, methacrylic acid hydroxyethyl ester and methacrylic acid hydroxypropyl ester. Most preferred is methacrylic acid hydroxyethyl ester.

The second reaction product is preferably essentially a monoacrylated urethane, but also another di- or polyhydroxy compound selected from glycols and amines such as ethylene, propylene, diethylene and butylene gelylcol or Chain length can be extended with amines. The most preferred chain extender is 1,4-butylene gellicol.

Preferred alkylene isocyanatoacrylates for R1 are selected from various compounds according to the invention. Examples of such preferred compounds include incyanatoalkylene methacrylate, most preferably incyanatoethyl methacrylate.

In the present invention, the polymerizable oligomer or the compound formed therefrom is preferably included in a composition that is a dental impression material for forming an impression of mammalian living tissue and manufacturing a mold thereof. A particularly preferred composition is a dental impression material.

Preferably, the dental impression material composition of the present invention is substantially stable with respect to assuming a permanent memory shape when stored in the absence of actinic radiation. Preferably, the composition is stable when stored as a single component material in the absence of actinic radiation for extended periods of time, for at least 1 month, more preferably for 3 months, and most preferably for more than 6 months. Preferably, it is stable. - component means that the dental impression material can be stored in its precise shape, so that when used by a dentist, the dentist can preferably apply the composition on the surface on which the impression is to be made; You won't have to do anything other than mold it.

Preferred embodiments for storage-stable impression materials are photoinitiated materials. The photoinitiation system can be any of a number of systems known in the art to promote polymerization of unsaturated acrylic groups when activated by actinic radiation at appropriate wavelengths, intensities, and irradiation times. Good too. Such systems include, but are not limited to, camphoroquinone and other α,β-diketones used alone or in combination with transition agents such as secondary and tertiary amines; There are compounds that are sometimes known to catalyze the polymerization of acrylates.

Materials such as benzoin and benzoin methyl ether, which are known to be photopolymerization catalysts, are found in the electromagnetic spectrum U
While light in the V region is used to cure currently preferred polymers, UV light is generally considered undesirable in most cases.

In one aspect of the invention relating to photopolymerizable compositions activated with actinic radiation, the compositions contain filtered light with wavelengths restricted to the visible light range of about 360-600 nm for health and safety reasons. Preferably, it is one that can be rapidly cured using the same method. More preferably, the majority of curing is at 400
It is carried out using light that is within the ~500 nm region.

The amount and type of photoinitiator or sensitizer are selected taking into account the intensity of the light source, the activation wavelength and their own ability to initiate polymerization. It is typically used at a concentration of .001 to 10% by weight, preferably 0.01 to 5% by weight. Photoinitiation promoters such as tertiary amines can also be used, such as methylgetanolamine, jetanolamine, triethanolamine, 4-ethyldimethylaminobenzoate or 4-dimethylaminobenzonitrile. Typically used in amounts of 0.001 to 10%, preferably 0.01 to 5% by weight of the polymeric resin present.

Urethane polyacrylate (di- or triacrylate) prepolymers, which are preferred compounds for use in the dental impression material compositions of the invention, also form an independent aspect of the invention; therefore, the urethane polyacrylate polymers are
Dental impressions, such as pastes containing initiators such as benzoyl peroxide, fillers such as quartz, talc and silica, diluents such as polypropylene gelcol with a molecular weight of 4000, and stabilizers such as BHT (butylated hydroxytoluene). It is pointed out that more conventional types of curing systems used in materials may be used for the production of self-hardening dental impressions. The base paste correspondingly contains promoters such as dihydroxyethyl-P-)luidine, diluents such as polydimethylsiloxane, and fillers. “Self-hardening” means that the dental impression material, in its as-used form, hardens at a predetermined rate by an internal hardening activator that does not require external initiation, such as actinic radiation initiation, which constitutes a further preferred embodiment of the invention. It is also within the scope of the present invention to add actinic radiation-activated components to self-hardening dental impression materials, so that upon mixing they will harden in a typical self-hardening manner or will not harden with the use of actinic radiation. An accelerated dual curing system is obtained.

The impression material may be a viscous liquid or may be modified with fillers to form a more viscous paste or even putty-like substance. Such fillers should, in a further preferred embodiment, have suitable optical properties so as not to interfere with the transmission of actinic radiation through the material upon initiation with the photoinitiator system. The filler particles should have the appropriate size and surface area to achieve the desired viscosity.

Usually non-reinforcing fillers are used to adjust the viscosity,
Suitable materials include those having a surface area of less than 50 m21g, such as calcium carbonate, fused quartz powder,
Silica calcium aluminate powder, titanium dioxide,
Examples include zirconium silicate, aluminum silicate, cristobalite, and feldspar. A preferred filler is silicon dioxide, such as fused silica, especially in the case of visible light curing compositions. The filler may be pulverized by various means depending on the purpose of use, preferably into a particulate filler having a size of 0.001 to 10 QILm. Particularly preferred are particles with an average diameter of 0.01 to 40 #Lm.

Reinforcing fillers can be used in the compositions of the present invention. Preferred reinforcing fillers have a surface area of at least 50 m2/g and include hyperthermogenic silicon dioxide, silicic acid hydrogels dehydrated for structure maintenance, silicon dioxide aerogels, and precipitated silicon dioxide.

All of these fillers, but especially the reinforcing fillers,
If they have been pretreated, for example with dimethyl-halogensilanes, or if they have been prepared, for example, by reaction of an aqueous silica sol with organohalogensilanes,
or if rendered hydrophobic in other ways, they can have organosilyl groups on their surface.

Mixtures of different fillers can also be used. The non-reinforcing filler is used in a concentration of at least 20% by weight based on all prepolymers present, and the force reinforcing filler is suitably between 1 and 20% based on the total weight of all prepolymers present.
It is used at a concentration of 80% by weight. Preferred total filler content is from 5 to 95% by weight, more preferably from 20 to 90%, most preferably from 40 to 85% by weight in some applications, based on the total composition weight. An important consideration in the case of actinic radiation-curable compositions is that the amount and type of filler is selected so that the actinic radiation penetrates through the polymerizable material and polymerization occurs to the depth of the impression upon irradiation; However, the filler does not need to match the refractive index of the resin exactly.

The alkylbenzene sulfonyl titanate mixed with the radically polymerizable resin, polymerization initiator and filler forms an important aspect of the invention. A preferred alkylbenzenesulfonyl titanate is neoalkoxytridodecylbenzenesulfonyl titanate (titanium neoalkoxytris(dodecylbenzene)sulfonate). Titanates are believed to impart better homogeneity by improving filler and resin bonding. Titanate is most likely to have the effect of promoting radical polymerization of polymerizable resins to some extent even when acrylic crosslinking polymerization is initiated by low-energy visible light. The titanate is preferably o, oot~ in the total composition.
It is present in an amount of 2% by weight, more preferably 0.005-1% by weight, most preferably 0.01-0.5% by weight.

Other formulation aids can also be used. organic resin, e.g. PV
C powder, methacrylate polymer powder, polyethylene and others can also be used as suitable fillers and plasticizers.

The compositions of the present invention may be stabilized with the addition of hydroquinone, catechol and other similar well-known polymerization inhibitors for the polymerization of (meth)acrylate compounds. Other optional ingredients include pigments and flavoring agents. - As an example, the highly viscous substance may have a peppermint flavour. Additional plasticizers include, for example, siloxanes, silanes, phthalates, glycerides, and other materials known in the art. Such plasticizers are usually added to modify the hydrophobicity, the softness or hardness of the composition, its viscosity or stickiness, etc. Silanes, for example, are plasticizers that also act as binders for resin and filler particles.

Under normal circumstances, dental impression materials or compositions are commonly used in tooth enamel, amalgams, composite dental fillings, metal bridges, and other materials common to a variety of patients, so that the composition can satisfy relatively general uses. Preferably, the material is non-adhesive to other substances present. The composition must have non-stick, fast-peel properties upon or after changing from its fluid state to its memory or elastic shape upon curing.

Moreover, the composition must not harm the soft tissue structures within the patient's mouth, be substantially non-toxic when used, and not induce an allergic reaction of the substance in the patient as a whole. Not only must the composition be easily removable from the soft tissue, but it must also accurately remember the soft tissue shape due to the permanent elastic memory shape of the impression.

A preferred aspect of the present invention also relates to the use of the novel compositions of the present invention for application to mammalian living tissue and to harden the material upon contact with the mammalian living tissue to form an impression thereof.

The novel composition, which constitutes a preferred aspect of the present invention in a preferred embodiment, has the most preferred use in a method of forming a dental impression in the oral cavity. A composition that is flowable, at least substantially memoryless, and capable of exhibiting permanent elastic memory in response to actinic radiation is brought into close contact with the surface on which the dental impression is to be made. To this end, in a preferred embodiment, the tray of composition is kept facing the surface until some of the composition has been poured and the composition is in good contact with the surface to be memorized. Preferably, the tray is maintained in positionally stable contact with the composition, and the actinic radiation is transmitted through at least a portion of the tray, after which the composition assumes a permanent elastic memory shape. The photopolymerization of the composition is activated to It has been found that impressions can be made on wet surfaces, ie oral fluids do not need to be removed and have no deleterious effects.

Preferred trays transmit actinic radiation through all of their bodies to the composition. For this purpose, the tray may be transparent plastic.

In a preferred embodiment, the Bokuto method also includes aspects related to materials that can exhibit the necessary effects for the preferred implementation of the preferred method of the present invention. A preferred method does not require premixing of the composition before use. The composition is preferably fluid, deformable and substantially free of any shape memory prior to actinic radiation activation so that it can form a dental impression, such as on adjacent soft tissue surfaces within the oral cavity. Preferred compositions assume a permanent elastic memory shape in response to actinic radiation. Permanent elastic memory shape means that the dental impression material is removed from the tooth by stretching and deforming it, usually through the application of manual force; specifically, the material can be peeled off from the tooth while retaining the memory shape of the tooth. It means that.

The one-component composition of the present invention can be stored in various ways such as filling a syringe in advance,
From there, the dentist can apply the material directly onto the soft or hard tissue to be reproduced. The composition can be pre-loaded onto a dental impression tray and placed directly into the patient's mouth by the dentist, or it can be pre-filled into a collapsible tube and placed in the patient's mouth by the dentist. The material can also be extruded onto a dental tray that is transparent to actinic radiation. Importantly, the container or its packaging is metallic or otherwise impermeable to actinic radiation in such a way that the composition of the invention can be protected from actinic radiation prior to use by the dentist. It should be stored in a.

In a preferred embodiment of the invention, the dentist places a special tray filled with the composition of the invention on the patient's body in such a way that the impression material is in sufficient contact with the entire area of oral tissue where the impression is to be made. Place it in your mouth. In order to avoid the formation of air bubbles on the tissue surface or in the constriction area, the dentist may take an optional step before placing the filling tray in the patient's mouth, i.e. the dentist preferably applies the present invention by extrusion from a syringe. The liquid impression material can be applied to the tissue surfaces, particularly the contracted areas such as between the teeth, and then the filling tray can be placed.

After placement of the special tray, the polymerization of the impression material is initiated with actinic radiation and is preferably polymerized for 5 minutes, more preferably 2 minutes, and most preferably less than 1 minute. Actinic radiation was obtained from L, D, Caulk Co.
mpany) Brismetics Light (RRISM)
ETIGSf ] 1te) Visible light preferably from a light source such as a polymerization unit, which unit emits visible light from the tip of the unit light guide in the wavelength range of 400-500 nm and with an energy output of about 550 IIW/c112. radiates. Polymerization times vary depending on the intensity and wavelength of the light used, the amount of material to be polymerized, and the trays used. For example, the tray may be a special tray with the following structure.

The time required by the dentist and for which the patient must wait for polymerization or shaping is reduced from 8-10 minutes to less than 2 minutes, reducing the total time required for filling and curing of the one-component impression material of the invention. The time is reduced to only 2-3 minutes, compared to about 15 minutes in the case of conventional techniques requiring mixing with two-component impression materials.

The impression tray used for the composition of the invention must be capable of transmitting light to all areas of the impression material that are to be activated directly by actinic radiation.

One simple structure is simply a standard transparent plastic tray, in which the polymerization light can be transmitted directly from all substrate portions of the tray into the material within the tray.

A suitable tray is the subject of U.S. Pat. No. 4,553,938, and another suitable tray is U.S. Pat.
No. 032,803 and Attorney Docket No. 1592 filed in 1987. The tray has light guide means, such as a short solid light pipe rod, at the front of the transparent tray to transmit light from the light source to the tray. The light is then transmitted into the impression material by the tray itself. Light may be reflected or deflected directly into the material by the reflective tray surface. Such a reflective surface may be provided by a metallic mirror-like coating on the outer tray surface or by approximately 9
It is formed by a cut surface, groove or ridge of a geometric shape that reflects or polarizes light at an angle of 0.06. Cuts, grooves or ridges are formed on the external or internal tray surface.

Special impression trays are pre-filled with impression material and completely covered with metal foil plastic laminate material, which is partially opened to form an impression only during use; This prevents the material from being exposed to light. The metal foil has a dual function in that it provides a surface that prevents unwanted light irradiation and reflects light that subsequently enters the tray and causes polymerization.

It has been found that the impression material according to the invention is also suitable for dosing. For example, if the impression material is incompletely cured,
or if an insufficient amount of material has been dispensed onto the tray, low-viscosity impression material may be added to the tray and/or teeth even if a partial or incompletely cured impression is removed from the mouth. The impression may then be completed. The bond between the impression material in the tray and the added impression material is homogeneous and complete.

Preferred materials of the invention have special uses in dentistry, in addition to their most preferred use in the production of dental impressions. Dental impression means an inverse image of the intraoral tooth morphology that serves as a mold from which a denture is manufactured or a model for denture manufacturing is manufactured. The preferred materials of the invention also find use in methods for directly manufacturing dentures, where the term denture is meant to include parts of dentures. This provides a format for a completely new method of manufacturing dentures. A particularly preferred aspect of the present invention is a method of manufacturing dentures by restoring dentures that have been damaged or can no longer fit properly and/or comfortably.

The material is relatively soft and plastic, so it conforms to the contours of the gums; however, it is relatively strong and durable, so it stays in place and retains its shape, and is soft and flexible. Moreover, it does not disintegrate even when kneading force is applied.

The dentist removes a removable denture that no longer fits comfortably within the patient's mouth and applies a thin coating of one of the compositions of the invention to all areas of the denture that contact the patient's soft tissue. The dentist then inserts the denture into the patient's mouth and applies the composition to the surfaces of the oral cavity that are to be recreated as a new properly fitted denture area. It has at least virtually no memory and is fluid. The denture is pressed firmly in place until some of the composition flows and forms a good seal with the surface in order to mold the composition into a precise shadow impression of the intraoral surfaces, so that the composition adheres to the patient's surface. It becomes pressed against the tooth surface. The denture is then removed from the patient's mouth and cured by photoinitiating actinic radiation if the preferred actinic curing embodiment of the present invention is applied. It has been discovered that acrylic dentures can be pre-cured sufficiently to secure the liner to the denture and establish its shape by using Prismetics Light.

Preferred optical properties have already been described with respect to the actinic polymerization initiation of the preferred impression material embodiments of the invention. A very effective method of operation is the TRIAD light curing unit [
Dentsply International, Inc. (Dentgpl)
y International Inc.) during the insertion of dentures, in which actinic radiation is irradiated onto the negative impression composition by operation of the unit.

The composition is thereby photopolymerized until it assumes the permanent elastic memory shape of the pictorial image of the intraoral surfaces.

It will also be appreciated that the flowable composition is applied onto the surface of a removable denture to be aligned against the soft tissue in the oral cavity by pressing the composition onto the soft tissue surface. Actinic radiation outside the ambient scene is about 360 to about -600
Preferably, it is substantially limited to the visible 5 nm light spectrum. If not all is desired upon reinsertion, adjustments are easily made by removing or resecting portions of the lined denture and repeating the shaping process directly on the soft tissue.

Actinic radiation curable compositions of the invention are preferably commercially stable to assume a permanent memory shape when stored in the absence of actinic radiation. The composition is preferably non-toxic when used in the oral cavity, is storage stable as a component-based composition in the absence of actinic radiation for at least one month, and is irradiated by light filtered to limited wavelengths in the visible light range. Permanent elastic memory when irradiated for 1 minute to a depth of 1 inch.

It has been found that the polymers produced according to the present invention are suitable for use in a number of applications. For example, when using low molecular weight materials to provide a rigid structure, the polymers of the present invention may be used in personal (sports) mouthguards or
It can also be used to manufacture night guards (to prevent teeth grinding). Mouthguards or nightguards can be manufactured in much the same way as dental impressions. That is, the polymer is filled into the mouth to obtain an impression of the general shape of the mouth, and then the polymer is either photocured in the mouth or dispensed from the mouth and cured.

Although the poly-material is hydrophilic, it does not absorb excessive amounts of water and therefore remains usable in the mouth for long periods of time, for example when used as a soft denture liner or mouth guard. discovered.

As will be apparent to those skilled in the art, the polymers of the present invention may be used to stabilize dental appliances in the mouth; as tissue conditioner drug carriers for soft tissue treatment in the mouth;
Rubber dam clamp sealer (dam clasp 5
bemastatic retractors; impression materials for removable dentures; substances for fixing matrix bands and wedges in restorative operations; medical wound dressing materials; as an alternative to epoxy molds. ; As a pipe sealer (for example, for PVC);
As an oral covering for implants after a return visit to place posts and cores; as a protective covering for ortho brackets to prevent or minimize trauma; as a protective covering for pontic or temporary teeth; It can also be used as a translucent intraoral or direct cast; for the production of impressions for hearing aids; and for prosthetic applications, especially for the face.

Other uses will be readily apparent to those skilled in the art, both within and outside of dentistry.

The impression material can be filled immediately before use or in the factory with substances or agents that can be used to treat or alleviate gingival pain.

For example, anti-inflammatory agents, antibacterial agents, astringents such as aluminum chloride or epinephrine, and others can be used as necessary.

The invention will be explained in more detail by the following examples.

Example 1 A preferred incyanatoethyl methacrylate urethane methacrylate oligomer elastomeric prepolymer compound was prepared according to the following formulation: dibutyltin dilaure) 0.4170
g1.4-butanediol (BA'JF) 31
．． The 0g procedure was as follows: 1 mole of polypropylene glycol (2 equivalents of hydroxy)
is reacted with 2 mol of trimethylhexamethylene diinocyanate (4 equivalents of isocyanate) with dibutyltin dilaurate.

Add polypropylene glycol to molecular sieve (4A
) for 2 days. It was then placed in a 2 liter reactor. Introduction of stirring dry air into the reactor was started. Drop dibutyltin dilaurate into glycol,
Stirred. Trimethylhexamethylene diisocyanate was then added dropwise to the glycol catalyst mixture via a separatory funnel. The addition was carried out at room temperature and the rate of addition was controlled to keep the temperature below 50°C. After about 3 hours, all the diisocyanate was added.

The mixture was stirred in a heating mantle (no heat) around the reactor overnight. The next day, 45 g of HEMA was added dropwise, and the dropping rate was controlled again while keeping the temperature inside the vessel below 50°C. After all the HEMA was added, 1,4-butanediol was added dropwise to the reactor contents. This mixture was stirred overnight.

The next day, incyanatoethyl methacrylate was added dropwise from the separatory funnel and stirred. A slight excess of HEMA (5 g) was added at about 3 oz after the last addition of isocyanatoethyl methacrylate to ensure that all free isocyanate was reacted.
After some time had passed, I finally added it to the container. The internal organs were stirred for 24 hours and then removed.

Example 2 A dental impression composition was formulated by manually mixing the following formulation under ambient conditions.

Resin of Example 1 100 Parts by weight Camphoroquinone 0.15 77 The dental impression composition was then tested for its relevant properties with the following results: The composition was approximately 5 cm (approx. 2 inches) apart, containing light in the visible spectrum.
General Electric 117 (Gen)
The sample was irradiated for 5 minutes using an EBV photo flood lamp. The material cured to an elastic solid. The test results below are for cases where irradiated and hardened dental impression materials are tested as described above.

The dental impression-making compositions were prepared in accordance with the American Dental Association (ADA) Instructions No. 19 (1984) for non-aqueous elastomeric impression materials:
The seed formulation was formulated by manual mixing.

Catalyst paste was manufactured according to the following formulation: 1. Resin
52.05 parts by weight 2, benzoyl peroxide 1., 04〃3, filler
27, 33 tt5, BHT(
butylated hydroxytoluene) 0.08 t
The basic paste was manufactured according to the following formulation: 1. Resin
51.80 parts by weight 3 and filler 27.20 tt The two types of paste were placed on parchment paper in equal proportions with a spoon and mixed for about 45 seconds. The material has a Shore A hardness of 55 at ambient temperature for 6 minutes.
(ASTMI 9.

1984 test method) to an elastic solid.

Below are the results of testing this material according to ADA Instruction No. 19 described in Example 2.

The material was found to be compatible with gypsum and the replication accuracy was excellent when tested according to ADA Instruction No. 19 for non-aqueous elastomeric materials.

Example 4 Another preferred incyanatoethyl methacrylate urethane methacrylate oligomer elastomer prepolymer compound was prepared by the following formulation.

Trimethylhexamethylene diisoanate (Torson Chemicals) 87.7g
Stannous octoate 0.50g1
．． 4-Butanediol (BASF) 18.7
g Isocyanatoethyl methacrylate 3L8g The procedure was as follows: Theoretically, 2 moles of trimethylhexamethylene diisocyanate (4 equivalents of isocyanate) using stannous octoate catalyzed by 1 mole of polypropylene glycol (2 equivalents of hydroxy). ) to react.

Polypropylene glycol was placed in a 2 liter reactor. Stirring and introducing dry air into the reactor was started. Stannous octoate was added into the reactor and stirred. Trimethylhexamethylene diisocyanate was then added dropwise to the glycol catalyst mixture via a separatory funnel. The addition was carried out at room temperature and the temperature was controlled to be below 50°C.

Addition was completed after 30 minutes. The contents were stirred for an additional 30 minutes. A sample was taken and titrated to determine the incyanate content. Incyanate was found to be 1.8%, indicating completion of the reaction of polypropylene glycol and trimethylhexamethylene diisocyanate. 27.1 g of HEMA was then added all at once into the reactor contents at a temperature of about 40°C. The contents were stirred for 45 minutes. A titration sample was then taken and the incyanate content was 0.85%. This means 1.4
The reaction between the isocyanate-terminated prepolymer and HEMA was completed, leaving 1 equivalent of isocyanate sites to react with -butanediol. At this point, 7 g of 1,4-butanediol 1B was added all at once to the reactor contents and stirred for 2 hours. The temperature inside the reactor was 4 during this operation.
The temperature was maintained at 0-50°C. After 2 hours, isocyanatoethyl methacrylate was added into the reactor via a separatory funnel. This addition took approximately 30 minutes. Stirring was continued until the next morning to ensure all free isocyanate had reacted. Then, the internal organs were removed.

Example 5 A dental impression composition was formulated by manually mixing the following formulation under ambient conditions.

Resin of Example 4 12.27g camphoroquinone 0.031g butylated hydroxytoluene 0.025g cristobalite filler 9.83g blue pigment [Dayglo] 0.035g alkyl benzyl phthalate) 0.88g The composition was treated with visible light. 500 watts GE containing light from the spectrum
A photoflat lamp was used to irradiate the dental impression composition sample with the lamp approximately 5 cm (approximately 2 inches) away. The material cured to an elastic solid.

Example 6 A dental impression composition was formulated by manually mixing the following formulation under ambient conditions.

Resin of Example 4 39.0 g Peppermint oil 0.20 g Blue pigment (Diglow) 0.080 g Feldspar
35.5 g camphoroquinone 0.10 g 4-dimethylaminobenzonitrile 0.24 g The composition was irradiated for 1 minute using the photoflood lamp operation of Example 2. The material hardened to an elastic solid.

Cure depth was tested using the Presmetics Light. A sample with a material thickness of 20 mm was coated with transparent Mylar approx.
．． It was covered with a sheet approximately 1 mil thick.

The sheet was in direct contact with the sample. The light was directed directly onto the Mylar paper. Light irradiation was for 10 seconds. Curing was determined to a depth of 8 mm by wiping uncured material from the bottom of the sample and measuring the remaining cured material.

Example 7 A dental impression forming composition with the following formulation was compounded in a double planetary mixer under reduced pressure.

Resin of Example 4 45.138g camphoroquinone 0.09g 4-dimethylaminobenzonitrile 0.4g butylated hydroxytoluene 0.05g fused silica
43. Bg pyrogenic silica (same as Example 6) 7.8g green pigment (Diglow)
0.10g blue pigment (Diglow)
0.02 g of the composition was irradiated with light for 40 seconds using the photoflood lamp operation of Example 2. The material cured to a rubbery solid.

When the hardening test method of Example 6 was carried out and the depth was measured, the hardening depth was 13 to 14 mm. The material was tested according to ADA Description Blind No. 19 described in Example 2 and exhibited the following physical properties. Example 8 The procedure of Example 7 was repeated except that the formulation was as follows.

Resin of Example 4 39.64g camphoroquinone 0.08g 4-ethyldimethylaminobenzo 0.24g ethylbutylated hydroxytoluene 0.04g fused silica 43.74g blue pigment (DeGlow) 0.07g The composition was treated with light by the procedure of Example 7. Irradiated.

The material cured to a hard but rubbery solid and when tested according to ADA Instruction Manual No. 19 described in Example 2, exhibited the following physical properties.

A dental impression forming composition having the following composition was blended under reduced pressure using a double planetary mixer.

Resin of Example 4 3130.41g
Camphoroquinone 0.79 g Butylated hydroxytoluene 0.170 g 4-dimethylaminobenzonitrile 3.83 g Fused quartz of Example 7 437.3 g Magenta pigment (
DeGlow) 0.80g Pyrogenic Silica (
Same as Example 6) 1313.13 g (Same as Example 6) The composition was tested for cure depth according to the procedure of Example 6 and the result was 19-20 mm. The composition was irradiated for 40 seconds with a Pris Sutix light using a Mylar spacer and a wide tip pressed directly onto the sample of the dental impression composition. The material cured to a rubbery solid and when tested according to ADA Instruction No. 19 described in Example 2, exhibited the following physical properties.

Example 1O A dental impression-forming composition having the following formulation and injectable viscosity was compounded in a double planetary mixer under reduced pressure.

Resin of Example 4 45B, 1 g camphoroquinone 0.92 g Butylated hydroxytoluene 0.20 g 4-dimethylaminobenzonitrile 2.81 g Blue pigment (Diglow) 2.514 g Fused quartz of Example 7 434.8 g Pyrogenic silica (practical) Same as Example 6) 75.9g composition was tested for cure depth according to the procedure of Example 6 and results were 15-
It was 16 mm. The composition was illuminated with Bliss' Takes Light for 40 seconds using a Mylar spacer and pressing a wide tip directly onto the sample of the dental impression composition. The material cures to a rubbery solid and the AD described in Example 2
When tested according to A Instruction Manual No. 19, the following physical properties were shown.

Example 11 stannous octoate 0.05$1.4
-Butaneshi*-,lz 4.29%TI
N (TMDI and HENA(7) reaction product)
8.10$HE M A
1.82% phosphoric acid-aqueous solution (1:1)
0.0021% polypropylene glycol (Poranol 2120) with an average molecular weight of 2000 is first mixed with the phosphoric acid solution. This is to neutralize the residual base in the polypropylene glycol that can act as a catalyst in the prepolymer reaction with TMD I. Then stannous octoate is added as a catalyst for urethane production. % excess of TMD I is added to produce an incyanate terminated prepolymer. A portion of the remaining isocyanate is then converted into HEM.
Block with A. The remaining portion is chain lengthened with 1,4-butanediol. Then add TIM. TIM is TMD
11 moles (2 equivalents) and 1 mole of HEMAI (1 equivalent) of the reaction product. It has one free incyanate and one methacrylate end in reaction path r.

The isocyanate moiety reacts with the hydroxyl groups remaining from the 1,4-butanediol. Finally, a small amount of HEMA
is added to react all residual isocyanate.

A comparison of moles and equivalents of each component is as follows.

i Excretion l Polanol 2120 1 2TMD
I 2 4HEMA
0.7 0.71.4-Butanediol 1.4 2.8TIM
O,70,7HEMA
O,40,4 activated resin Above resin 88.78X camphoroquinone 0.20$4-
Dimethylaminobenzonitrile 0. θ2z Butylated hydroxytoluene (BIT) 0.10% High viscosity tray material Above activated resin 45.95g Fused quartz (average particle size 15-25 μm) 42.37
g Aerosil R-972 Pyrogenic Silica! 3.04
% DeGlow A-21 Corona Magenta Mu 0.08
24% Para f/-Lua 11P (Sea 07-9-1
17 2. OO$lukylphthalate) Care! , +71 TO LIcA 89
0.05$ γ-methacryloxyprobilt 0.
50% Rimethoxysilane viscous injectable material Activated resin 54.78 g Fused quartz (average particle size 15-25 ti-m) 311
．． 88X Aerosil R-972 Pyrogenic Silica 1
．． 55g DeGlow A-19 Horizon Blue Pigment 0.
25$ Ha5 Chi/-Lua 11P (C G7-q-+
+7 3.10% Lucyl Phthalate) /r7- IJ7ri) LICA 09
0.13$γ-methacryloxyprobilt 0.
52% Rimethoxysilane The attached table shows comparative values for the properties of this example material based on the ADA instructions.

A material made by combining any of the resins has the advantage that there is no restriction on working time, no mixing is required, it cures at will, and it cures quickly.

Moreover, the impression has good legibility and is hydrophilic so that it can be poured immediately into plaster or epoxy.

In a preferred embodiment, peppermint may be added into the highly viscous material.

Example 12 The resin of Example 11 was compounded under reduced pressure according to the following formulation,
High and low viscosity impression pastes were obtained.

On L1 11 Σ: On L1 Example 1117) Resin 45.31! Camphoroquinone 0.092$4-
Dimethylaminopenzoni) 0.422% Butylated hydroxytoluene 0.0459% Fused quartz powder (average particle size 15-25 pm) 43.72%
Aerosil R-972 Pyrogenic Silica 7.50% DeGrow Corona Magenta Pigment 0.082 and Peppermint Oil 0.20$ Ken-! J
7ri) LIGA 09 0.10! Example 1117) Resin 55.231 Camphoroquinone 0.11! 1i4-Dimethylaminobenzonitrile 0.5196 Butylated Hydroxytoluene 0.11! Fused quartz powder (average particle size 15-25 μm) 37.63! l; Aerosil R-972 pyrogenic silica 2.424! Dayglo One Horizon Blue Pigment 0.25! lliken react LICA 09 0.13! Example 13 An isocyanatoethyl methacrylate urethane methacrylate oligomer elastomer prepolymer compound was prepared according to the formulation and procedure of Example 4. This resin was then compounded under reduced pressure according to the following formulation.

Resin of Example 4 46.054J camphoroquinone 0.0934 to 4
-Dimethylaminobenzonitrile 0.27996 Butylated hydroxytoluene 0.046! ! Silanized fused silica 43.5444 Pyrogenic silica (Aerosil R-972) 7.563! To DeGlo blue pigment 0.0674 to peppermint oil 0.15! ! Three-dimensional transformation samples of the above materials were prepared in the preferred ADA Instruction No. 19 mold by curing for 1 minute under the photoflood lamp of Example 2. After curing, the sample was removed from the mold and the length on the line was read according to ADA Manual No. 19. After this direct reading, each sample was immersed in deionized water 250rnJZ and stored at 37°C. Samples were taken periodically and the length on the prescribed line was read and recorded. The rate of change was calculated and shown in the table below, which describes the dimensional stability of the material over time in a humid environment.

Moreover, the material remained soft and flexible for 16 months in water.

Example 14 A non-staining VLC soft denture liner was manufactured according to the following procedure.

Highly viscous paste 1 was prepared in a double planetary mixer under reduced pressure using the resin of Example 11 according to the following formulation.

Resin of Example 11 45.3H camphoroquinone 0.0924 to 4-dimethylaminobenzonitrile 0.422! I; Butylated hydroxytoluene 0.04H fused quartz powder (average particle size 15-25 μm) 42.37! Pyrogenic silica (Aerosil R-972) 9.044I
i-day glow corona magenta pigment 0.0829
6 Palatinol 711P 2. OH
Ken React LICA 09 0.19
13 Paste 2 was prepared manually using silicone methacrylate resin according to the following formulation.

4-dimethylaminobenzonitrile 0.424J camphoroquinone 0.092! butylated hydroxytoluene 0.023'! Fused quartz powder (average particle size 15-25 μm) 42.37!
Pyrogenic silica (Aerosil R-972) 9.0
4! l; Deglo Corona Magenta Pigment 0.0
80! Ken React L/I (:A 09
0.10! Palatinol 711P
2.00! γ-methacryloxypropyltri 0.50! Next, 125 parts of methoxysilane and paste were manually mixed with 225 parts of paste to obtain Paste 3.

Paste 1.2 and 3 disks are 3mmX20mm
Photo flood lamp bottom 30 in stainless steel ring
Manufactured by curing in seconds. These samples were then soaked in coffee and tea for 24 hours at 37°C. After removal from coffee and tea, the discs were washed and dried with absorbent paper. The samples were visually inspected for coloration. Paste 1 was heavily colored. paste 3
was lightly to moderately colored.

Paste 2 was only slightly colored and gave the best results. Testing of the discs revealed that Paste 3 gave the best results with its combination of low coloration and elastic properties. Paste 2 was too hard and brittle when cured into a good soft denture liner.

Although we have described what are believed to be the preferred embodiments of this invention under patent law, it will be apparent to those skilled in the art that numerous changes and improvements can be made without departing from this invention and, therefore, the patent claims. is intended to embrace all such equivalent variations as fall within the true spirit and scope of the invention.

Claims (1)

[Claims] 1. Compound of the following general formula: R_1-[A]-R_1 [In the above formula, R_1 is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼ Yes, in the above formula, R_1 may be the same or different; R_
3 is H, alkyl having 2 to 10 carbons, substituted alkyl having 2 to 10 carbons, aryl having 6 to 14 carbons, substituted aryl having 6 to 14 carbons, F, CN, and R_3 may be the same or different at each position. Also good; R_4 is a divalent hydrocarbon group or a divalent substituted hydrocarbon group, but has 2 to 100 carbon atoms.
may be linear or branched or cyclic, or a combination thereof; and [A] is polyurethane;
A new structure of a substance consisting of the main chain of polyether or polyester. 2. The general formula A is [R_5]-X-[R_6] (R_5 and R_6 are each a divalent hydrocarbon group or a divalent substituted hydrocarbon group, and even if it is linear, branched, or cyclic, a combination thereof may be siloxane or substituted siloxane, X is polyurethane, R_
5-X and R_6-X are connected by a urethane bond, and may have any hydrocarbon or substituted hydrocarbon group, and may be linear, branched, or cyclic, or a combination thereof. , and even one or more of the following groups, i.e. siloxanes, substituted siloxanes, sulfones, etc., but preferably polyethers, polyesters or combinations thereof, most preferably X is a polyether. Therefore, the polyether group is a straight chain. R_5 and R_6 have 2 to 100 carbons],
A novel structure of the substance according to claim 1. 3. [A] is ▲There is a mathematical formula, chemical formula, table, etc.▼, or [A] is ▲There is a mathematical formula, chemical formula, table, etc.▼ (In the above formula, R and R_8 are alkylene with 2 to 25 carbon atoms and X is 10 to 100). 4. Compounds with the following general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above formula, R_7 is alkylene, substituted alkylene, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R_8 is carbon 2 ~ 8 alkylene,
R is alkylene having 2 to 25 carbon atoms, and X is 10 to 10
0)] A novel structure of the substance according to claim 1. 5. A novel structure of the material of claim 1 containing an initiator activated by actinic radiation in the visible light range from about 360 to about 600 nanometers. 6. The structure is a dental impression material, which is non-toxic when used in the oral cavity, is stable when stored as a one-component composition in the absence of actinic radiation for at least one month, and is substantially 1 to a depth of about 2.5 centimeters (1 inch) with light filtered to wavelengths restricted to the visible range.
A novel structure of material according to claim 1, which exhibits a permanent elastic memory when irradiated for minutes. 7. A novel impression material that is applied to mammalian tissue and cures to form an impression upon contact therewith, the impression material comprising radicals present in an amount of about 5-95% by weight of the total composition. Polymerizable resin; about 0.001 to total composition
Alkylbenzenesulfonyl titanate present in an amount of about 2% by weight; about 0.001 to about 10% by weight of the polymerizable resin
a polymerization initiator present in an amount of about 5 to 9 of the total composition;
A novel impression material characterized in that it consists of a filler present in an amount of 5% by weight. 8. The radically polymerizable resin is present in an amount of about 10 to 80% by weight of the total composition; the alkylbenzenesulfonyl titanate is a titanium IV neoalkoxytris(dodecylbenzene) sulfonate and is present in an amount of about 0.005 to 80% by weight of the total composition;
the polymerization initiator is present in an amount of about 0.01% to about 5% by weight of the polymerizable resin; and the filler is present in an amount of about 20% to about 90% by weight of the total composition. A novel impression material according to claim 7, which is present in 9. The novel impression material according to claim 8, wherein the polymerization initiator is a photoinitiator and the filler consists of silicon dioxide. 10. The radical-initiated polymerizable resin has the structure of the following general formula: R_1-[A]-R_1 (In the above formula, R_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R_1 may be the same or different; R
_3 is H, alkyl having 2 to 10 carbons, substituted alkyl having 2 to 10 carbons, aryl having 6 to 14 carbons, substituted aryl having 6 to 14 carbons, F, CN, and R_3 may be the same or different at each position. R_4 is a divalent hydrocarbon group or a divalent substituted hydrocarbon group, but may be linear, branched, or cyclic, or a combination thereof, and has 2 to 100 carbons) ( In the above formula, R is alkylene having 2 to 25 carbon atoms, and R
_8 is alkylene having 2 to 25 carbon atoms, and X is 10 to 1
00) The novel impression material according to claim 9, comprising: 11. The structure of the radical-initiated polymerizable resin is the following general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R_7 is alkylene, substituted alkylene, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula , R_8 is alkylene having 2 to 8 carbons,
R is alkylene having 2 to 25 carbon atoms, and X is 10 to 10
0)] The novel impression material according to claim 10. 12. (a) Clean the surface on which the impression is to be formed; (b) Apply to the surface a dental impression material containing a structure of the following general formula, R_1-[A]-R_1 [in the above formula] , R_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R_3 is H, alkyl, substituted alkyl, aryl, substituted aryl, F, CN) R_3 may be the same or different at each position; R_4 is a divalent hydrocarbon group or a divalent substituted hydrocarbon group, and may be linear, branched, or cyclic, or a combination thereof. [A] is a main chain of polyurethane, polyether or polyester]; (c) curing the dental impression material while bringing it into close contact with the surface to be formed; and (d) curing the dental impression material; removing said hardened dental impression material from the surface; a method of forming a dental impression of a region in the oral cavity; 13. The radical polymerizable resin is the following general compound: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above formula, R_7 is alkylene, substituted alkylene, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R is an alkylene of 2 to 25 carbon atoms and Approximately 0.005 of the composition
further comprising a titanium IV neoalkoxytris(dodecylbenzene) sulfonate in an amount of from about 1% by weight; a polymerization initiator is present in an amount from about 0.01 to about 5% by weight of the polymerizable resin; and a filler from about 20 to about 90% by weight of the total composition
13. The method of claim 12, wherein: 14. The method according to claim 13, wherein the polymerization initiator is a photoinitiator and the filler is silicon dioxide. 15. Compound R_1-[A]-R_1 [In the above formula, R_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and in the above formula, R_1 may be the same or different; R_3 is H, alkyl of 2 to 10 carbons, substituted alkyl of 2 to 10 carbons, aryl of 6 to 14 carbons, 6 to 14 carbons;
Substituted aryl, F, CN, R_3 may be the same or different at each position; R_4 is a divalent hydrocarbon group or a divalent substituted hydrocarbon group, but may be linear or branched or cyclic. or a combination thereof, and has from 2 to 100 carbons; [A] is a main chain of polyurethane, polyether or polyester. 16. [A] is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R is alkylene with 2 to 25 carbons, and R
_8 is alkylene having 2 to 25 carbon atoms, and X is 10 to 1
00), the soft denture liner according to claim 15. 17. A novel structure of the substance according to claim 1, wherein the general formula A in the compound is [R_5]-X-
[R_6] [R_5 and R_6 are each a divalent hydrocarbon group or a divalent substituted hydrocarbon group, X is polyurethane, polyether or polyester, and R_5-X and R_6
-X is bonded by a urethane bond, and R
_5 and R_6 have 2 to 100 carbon atoms.] The soft denture liner according to claim 16. 18. Compounds with the following general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above formula, R_7 is alkylene, substituted alkylene, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R_8 is carbon 2 ~ 8 alkylene,
R is alkylene having 2 to 25 carbon atoms, and X is 10 to 10
0)] The soft denture liner according to claim 17. 19, the following formula: HMA-(OCN--NCO)-[O-PE-O]-(
NCO-NCO)-BD-[OCN--OCN-HMA
] [In the above formula, O-PE-O represents a hydroxy-substituted polyether, polyurethane or polyester, OCN and NCO represent an isocyanate group, and -(OCN-NCO)- represents a polyisocyanate, HMA is an unsaturated BD represents a lower alkyl diol] comprising: (a) about 1 equivalent of hydroxy substitution to form a polyurethane chain with two isocyanate end groups; The oligomer is reacted with about 2 equivalents of diisocyanate, and (b) the polyurethane formed in step (a) is reacted with about 2 equivalents of diisocyanate to form primarily a polyurethane having isocyanate groups on one end and an unsaturated organic acid ester on the other end. 1/2
(c) reacting the product of step (b) with said isocyanate groups to form a polyurethane having an unsaturated organic acid ester at one end and a hydroxyl at the other end; a reaction product of an unsaturated organic acid ester and a diisocyanate is formed in step (c) by reacting with a reacting lower alkyl diol to form a polyurethane having (d) an unsaturated hydroxy-substituted organic acid ester on at least two ends; 1. A manufacturing method comprising a continuous process of reacting with polyurethane. 20, PE is polyether, polyisocyanate is trimethylhexamethylene diisocyanate,
HMA is hydroxyethyl methacrylate and BD
The manufacturing method according to claim 19, wherein is butanediol.